CN103539928B - Titanium series polyester catalyst and the method for producing semi-dull polyester - Google Patents
Titanium series polyester catalyst and the method for producing semi-dull polyester Download PDFInfo
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Abstract
The present invention relates to a kind of method of titanium series polyester catalyst and production semi-dull polyester, the dibastic alcohol compound catalyst hydrolytic resistance that mainly solves to exist in the prior art obtained titanium is poor, solubility is low in ethylene glycol, the problem of obtained semi-dull hue of PET chip difference.The present invention is by using with titanium compound, dihydric alcohol and reaction product selected from least one of II B of A, V of the periodic table of elements II, II B metal salt compound, at least one aliphatic organic acid and at least one phosphate compound are catalyst, catalyst preparation pH value of reaction system is kept preferably to solve the problem for 4.5~6.5 technical scheme simultaneously, available in the polyester particularly industrial production of semi-dull polyester.
Description
Technical field
The present invention relates to a kind of titanium series polyester catalyst and using the method for the Catalyst Production semi-dull polyester.
Background technology
Polyethylene terephthalate（PET, hereinafter referred to as polyester）It is the kind of yield maximum in chemical fibre.With the whole world
The increasingly raising of economic growing and living standards of the people, textile clothing industry has obtained rapid development.And account for polyester
The features such as semi-dull polyester slice of total amount 90% is with its excellent dyeability, high intensity and excellent processing characteristics has been obtained extensively
General application, and application field will expand increasingly, the primary raw material as fields such as weaving fibre, polyester industrial films.It is poly-
The catalyst of Lipase absobed almost relate to all main subgroup elements in addition to halogens and inert element.Industry should at present
It is mainly antimony, three serial catalyst of germanium and titanium with the polyester catalyst more with research.
Antimony-based catalyst is catalyst most commonly used at present, and more than 90% polyester is by antimony acetate in the world
（SbAc3）, antimony oxide（Sb2O3）It is what Catalyst Production came out with antimony glycol, because antimony is heavy metal element, has
Certain toxicity, the preparation and processing of antimony-based catalyst, the process of polyester and polyester in the production process of polyester
Using being likely to adversely affect human body and environment with removal process.With the enhancing of people's environmental consciousness, to antimony
Limitation will be more and more stricter.
Germanium series catalysts have good stability, and side reaction is less during the course of the reaction, and obtained polyester colourity is good,
But it is due to that resource is few, it is expensive.
As the environmentally friendly catalyst for being most hopeful substitution antimony-based catalyst, titanium series polyester catalyst is to health
And ecological environment is without influence, and with higher catalytic activity, it can be all called from all multi-angles such as safety, cost, environment
Classic polymerization catalyst.It is a kind of main trend that titanium series polyester catalyst, which substitutes antimony catalyst, and external each major company pushes away in succession
Titanium series catalyst polyester product is gone out, such as without antimony PFY and polyester staple fibers, hot-filling bottle with without antimony polyester slice.This is right
The sustainable development of polyester industrial will bring the effect of greatly facilitating.
In conventional titanium series polyester catalyst preparation method, the stabilisation of titanium compound is widely studied, wherein the two of titanium
First alcoholic compound has also been received by domestic and international major research institutions because of its stable cyclic chelate structures, but such catalyst is past
Poor toward hydrolytic resistance, chemical combination structural instability, the solubility in ethylene glycol is low, and catalytic efficiency is not high, obtained polyester color
It is mutually still bad, do not solve polyester jaundice problem made from Titanium series catalyst.
The content of the invention
One of technical problems to be solved by the invention are the dibastic alcohol compounds that there is obtained titanium in the prior art
Catalyst hydrolytic resistance is poor, solubility is low in ethylene glycol, and there is provided one kind for the problem of obtained semi-dull hue of PET chip is poor
New titanium series polyester catalyst.The catalyst preparation is convenient, is the catalyst of homogeneous liquid, can be dissolved each other with ethylene glycol, with good
Good light durability and heat endurance, have form and aspect good using the polyester especially semi-dull type polyester of such Catalyst Production
Advantage.The two of the technical problems to be solved by the invention are to provide a kind of method for producing semi-dull polyester.This method has
The good advantage of obtained semi-dull type PET hue.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：A kind of titanium series polyester catalyst,
The reaction product of 0.5~10 hour is reacted at 0~200 DEG C including following raw material：
(A) there is the titanium compound of below general formula
Ti(OR)4
R is the alkyl selected from 1~10 carbon atom；
(B) it is selected from the dihydric alcohol with 2~10 carbon atoms；
(C) at least one of IA, IIA, VII B, II B metal salt compound in the periodic table of elements；
(D) selected from least one of organic acid aliphatic organic acid；
(E) selected from least one of phosphorus compound phosphate compound；
Wherein, the mol ratio of dihydric alcohol (B) and titanium compound (A) is 1~20: 1；Metal salt compound (C) is closed with titanizing
The mol ratio of thing (A) is 0.1~20: 1；The mol ratio of aliphatic organic acid (D) and titanium compound (A) is 0.1~20: 1；Phosphoric acid
The mol ratio of ester compounds (E) and titanium compound (A) is 0.1~10: 1；The pH value of reaction system is controlled 4.5~6.5.
In above-mentioned technical proposal, it is different that titanium compound is selected from tetramethoxy titanate ester, tetraethyl titanate, metatitanic acid orthocarbonate, metatitanic acid four
At least one of propyl ester or butyl titanate compound；Dihydric alcohol (B) is selected from ethylene glycol, 1,2- propane diols, 1,4- butanediols
Or at least one of 1,6-HD dihydric alcohol；Metal salt compound (C) IA, IIA, VII B, II in the periodic table of elements
At least one of B lithium, sodium, zinc, manganese, magnesium, calcium or cobalt metal salt；Aliphatic organic acid (D) be selected from citric acid, glacial acetic acid,
At least one of tartaric acid, oxalic acid or lactic acid aliphatic organic acid；Phosphate compound (E) is selected from trimethyl phosphate, phosphoric acid
At least one of triethyl, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, tributyl phosphate or triphenyl phosphate phosphate chemical combination
Thing.Raw material also includes (F) and is selected from the monohydric alcohol with 2~10 carbon atoms.
In above-mentioned technical proposal, the mol ratio preferred scope of dihydric alcohol (B) and titanium compound (A) is 1~4: 1, works as binary
When alcohol (B) is less than 1 with titanium compound (A) mol ratio, obtained catalyst water resistance is bad.Metallic compound (C) is closed with titanizing
The mol ratio preferred scope of thing (A) is 0.1~15: 1, and more preferably scope is 0.1~10: 1.Aliphatic organic acid (D) and titanizing
The mol ratio preferred scope of compound (A) is 1~15: 1, and more preferably scope is 1~10: 1.Phosphate compound (E) is closed with titanizing
The mol ratio preferred scope of thing (A) is 5~10: 1.The mol ratio of monohydric alcohol (F) and titanium compound (A) is 1~20: 1, more preferably
Scope is 1~10: 1.
In above-mentioned technical proposal, the reaction temperature preferred scope for preparing polyester catalyst is 10~180 DEG C, and the reaction time is excellent
It is 2~6 hours to select scope.Catalyst preferred scheme is homogeneous liquid catalyst, and more preferably scheme can dissolve each other with ethylene glycol
Homogeneous liquid catalyst.
In order to solve the above-mentioned technical problem two, the technical solution adopted by the present invention is as follows：One kind production semi-dull polyester
Method, using dicarboxylic acids and aklylene glycol as raw material, use titanium series polyester catalyst in reaction temperature for 230~280 DEG C,
Reaction pressure be normal pressure~0.5MPa under the conditions of carry out esterification, obtain esterification products, then reaction temperature be 250~
320 DEG C, reaction pressure obtains in polyester product, course of reaction for progress polycondensation reaction under the vacuum condition less than 150Pa and adds titanium
White powder is used as delustering agent；Titanium series polyester catalyst wherein used, including following raw material are 0~200 DEG C in reaction temperature
Under the conditions of, the reaction product of reaction 0.5~10 hour：
(A) there is the titanium compound of below general formula
Ti(OR)4
R is the alkyl selected from 1~10 carbon atom
(B) it is selected from the dihydric alcohol with 2~10 carbon atoms
(C) at least one of IA, IIA, VII B, II B metal salt compound in the periodic table of elements；
(D) selected from least one of organic acid aliphatic organic acid；
(E) selected from least one of phosphorus compound phosphate compound；
Wherein, the mol ratio of dihydric alcohol (B) and titanium compound (A) is 1~20: 1；Metal salt compound (C) is closed with titanizing
The mol ratio of thing (A) is 0.1~20: 1；The mol ratio of aliphatic organic acid (D) and titanium compound (A) is 0.1~20: 1；Phosphoric acid
The mol ratio of ester compounds (E) and titanium compound (A) is 0.1~10: 1；The pH value of catalyst preparation reaction system is controlled 4.5
~6.5.
In above-mentioned technical proposal, dicarboxylic acids be selected from terephthalic acid (TPA), phthalic acid, M-phthalic acid, naphthalenedicarboxylic acid,
At least one of biphenyl dicarboxylic acid or cyclohexane dicarboxylic acid, preferred scheme are terephthalic acid (TPA)；Dihydric alcohol is selected from ethylene glycol, 1,
At least one of ammediol, BDO, 1,6- hexylene glycols and 1,4-CHDM, preferred scheme are second two
Alcohol.
The preparation method of titanium series polyester catalyst of the present invention is as follows：
It is Ti (OR) by formula4The obtained product of titanium compound and diol reaction with the periodic table of elements IA,
IIA, VII B, II B at least one metal salt compound, at least one aliphatic organic acid and at least one Phosphation
Compound reacts, and obtains homogeneous liquid titanium polyester catalyst.
Method prepared by polyester of the present invention is as follows：
Can using known preparation process of polyester, using dicarboxylic acids and dihydric alcohol as raw material, in reaction temperature be 230~
280 DEG C, reaction pressure obtains prepolymer to carry out esterification under the conditions of normal pressure~0.5MPa, is then 250 in reaction temperature
~320 DEG C, reaction pressure obtains polyester product, titanium series polyester catalyst to carry out polycondensation reaction under the vacuum condition less than 150Pa
It can be added before addition before esterification starts can also start in polycondensation reaction.
Titanium dioxide is added in course of reaction as delustering agent, the addition of titanium dioxide is 0.3%（Based on prepared polyester
Weight）, titanium dioxide select after esterification products are obtained, start vacuum polycondensation before be added in reactor.
In the present invention, inherent viscosity and form and aspect of polyester etc. are tested by the following method：
1）Inherent viscosity：Phenol tetrachloroethane mixed liquor is made to use determination of ubbelohde viscometer at a temperature of solvent, 25 DEG C.
2）Form and aspect：Pellet sample uses the automatic aberration of color-view of BYK Gardner companies after being handled 1 hour at 135 DEG C
Meter determines its Hunter L value（Brightness）, a values（Yellow-blue form and aspect）With b values（The form and aspect of red-green）.Wherein, L values are higher, brightness
It is bigger；The high then polyester slice of b values is partially yellow.For the present invention, it is desirable to pursue high L values, low b values.
The present invention is Ti (OR) by using by formula4Titanium compound, dihydric alcohol, in the periodic table of elements IA,
At least one of IIA, VII B, II B metal salt compound, aliphatic organic acid and phosphate compound reaction obtain homogeneous
Liquid titanium polyester catalyst.Surprisingly, it was found that in the case where catalyst contains salt and organic acid compound,
The pH value of reaction system is controlled 4.5~6.5, prepared catalyst Ti compound particle reaches nanoscale and water resistant
Solution, stability is superior, and apparent presentation colorless clear liquid dissolves each other with ethylene glycol, with antimony catalyst under the same conditions, obtained half
Extinction type polyester has good form and aspect, achieves preferable technique effect.
Below by embodiment, the invention will be further elaborated.
Embodiment
【Embodiment 1】
Catalyst A preparation
28.4 grams of tetraisopropyl titanate is added in the reactor equipped with agitator, condenser and thermometer（0.1 mole）,
12.4 grams of ethylene glycol is slowly dropped into reactor（0.2 mole）, reacted 2 hours at 70 DEG C, the white emulsion form of system, plus
Enter 107 grams of four acetate hydrate magnesium（0.5 mole）, lactic acid 36g（0.4 mole）With 45.5 grams of triethyl phosphate（0.25 mole）, survey
It is 5.5 to obtain system pH, reacts 2 hours, obtains homogeneous clear liquid, be catalyst A.
The preparation of polyester
By 500 grams of terephthalic acid (TPA)s and 316 grams of ethylene glycol and catalyst A（The amount of polyester based on generation, the weight of titanium atom
Measure as 5ppm）, mix and be made into slurry, be added in polymeric kettle, carry out esterification, esterification temperature is 230~255 DEG C, pressure
For 0.25MPa, the water for reacting generation is discharged by rectifier unit.Normal pressure is down in esterification after terminating, add 3.15 grams of titanium dioxide
Content is 55% titanium dioxide/ethylene glycol slurry, vacuumizes and is decompressed to system pressure less than 130Pa, simultaneous reactions temperature gradually rises
It is afterwards that reaction product is continuous with bar shaped from polymeric kettle bottom when system is reacted to reaction is stopped after reaching 150min to 280 DEG C
Extrusion, cooling, pelletizing, for performance test.
Test result is shown in Table 1.
【Embodiment 2】
Catalyst B preparation
28.4 grams of tetraisopropyl titanate is added in the reactor equipped with agitator, condenser and thermometer（0.1 mole）,
12.4 grams of ethylene glycol is slowly dropped into reactor（0.2 mole）, reacted 2 hours at 70 DEG C, the white emulsion form of system, plus
Enter 110 grams of zinc acetate（0.5 mole）, lactic acid 36g（0.4 mole）With 35 grams of trimethyl phosphate（0.25 mole）, measure system pH
It is worth for 5.5, reacts 2 hours, obtain homogeneous clear liquid, be catalyst B.
The preparation of polyester
Polyester is prepared by method similarly to Example 1, catalyst is used as using catalyst B（Polyester amount based on generation）
The weight of titanium atom is 5ppm.
Test result is shown in Table 1.
【Embodiment 3】
Catalyst C preparation
28.4 grams of tetraisopropyl titanate is added in the reactor equipped with agitator, condenser and thermometer（0.1 mole）,
12.4 grams of ethylene glycol is slowly dropped into reactor（0.4 mole）, reacted 2 hours at 70 DEG C, the white emulsion form of system, plus
Enter 128 grams of magnesium lactate（0.5 mole）, lactic acid 36g（0.4 mole）With 35 grams of triethyl phosphate（0.25 mole）, measure system pH
It is worth for 5.5, reacts 2 hours, obtain homogeneous clear liquid, be catalyst C.
The preparation of polyester
Polyester is prepared by method similarly to Example 1, catalyst is used as using catalyst C（Polyester amount based on generation）
The weight of titanium atom is 5ppm.
Test result is shown in Table 1.
【Embodiment 4】
Catalyst D preparation
28.4 grams of tetraisopropyl titanate is added in the reactor equipped with agitator, condenser and thermometer（0.1 mole）,
12.4 grams of ethylene glycol is slowly dropped into reactor（0.2 mole）, reacted 2 hours at 70 DEG C, the white emulsion form of system, plus
Enter 154 grams of calcium lactate（0.5 mole）, glacial acetic acid 24g（0.4 mole）With 53.2 grams of tributyl phosphate（0.2 mole）, measure system
PH value is 5.4, reacts 2 hours, obtains homogeneous clear liquid, be catalyst D.
The preparation of polyester
Polyester is prepared by method similarly to Example 1, catalyst is used as using catalyst D（Polyester amount based on generation）
The weight of titanium atom is 5ppm.
Test result is shown in Table 1.
【Embodiment 5】
Catalyst E preparation
28.4 grams of tetraisopropyl titanate is added in the reactor equipped with agitator, condenser and thermometer（0.1 mole）,
12.4 grams of ethylene glycol is slowly dropped into reactor（0.2 mole）, reacted 2 hours at 70 DEG C, the white emulsion form of system, plus
Enter 154 grams of manganese acetate（0.5 mole）, glacial acetic acid 24g（0.4 mole）With trimethyl phosphate 28g（0.2 mole）, measure system pH
It is worth for 5.4, reacts 2 hours, obtain homogeneous clear liquid, be catalyst E.
The preparation of polyester
Polyester is prepared by method similarly to Example 1, catalyst is used as using catalyst E（Polyester amount based on generation）
The weight of titanium atom is 5ppm.
Test result is shown in Table 1.
【Embodiment 6】
Catalyst F preparation
28.4 grams of tetraisopropyl titanate is added in the reactor equipped with agitator, condenser and thermometer（0.1 mole）,
12.4 grams of ethylene glycol is slowly dropped into reactor（0.2 mole）, reacted 2 hours at 70 DEG C, the white emulsion form of system, plus
Enter 43 grams of sodium acetate（0.5 mole）, glacial acetic acid 24g（0.4 mole）With trimethyl phosphate 28g（0.2 mole）, measure system pH
For 5.4, react 2 hours, obtain homogeneous clear liquid, be catalyst F.
The preparation of polyester
Polyester is prepared by method similarly to Example 1, catalyst is used as using catalyst F（Polyester amount based on generation）
The weight of titanium atom is 5ppm.
Test result is shown in Table 1.
【Embodiment 7】
Catalyst G preparation
Absolute ethyl alcohol 50g and tetraisopropyl titanate are added in the reactor equipped with agitator, condenser and thermometer
28.4 grams（0.1 mole）, 12.4 grams of ethylene glycol is slowly dropped into reactor（0.2 mole）, reacted 2 hours at 70 DEG C, body
It is white emulsion form, adds 107 grams of four acetate hydrate magnesium（0.5 mole）, lactic acid 36g（0.4 mole）And triethyl phosphate
45.5 grams（0.25 mole）, it is 5.5 to measure system pH, reacts 2 hours, obtains homogeneous clear liquid, be catalyst G.
The preparation of polyester
Polyester is prepared by method similarly to Example 1, catalyst is used as using catalyst G（Polyester amount based on generation）
The weight of titanium atom is 5ppm.
Test result is shown in Table 1.
【Embodiment 8】
Catalyst H preparation
Absolute ethyl alcohol 50g and tetraisopropyl titanate are added in the reactor equipped with agitator, condenser and thermometer
28.4 grams（0.1 mole）, 12.4 grams of ethylene glycol is slowly dropped into reactor（0.2 mole）, reacted 2 hours at 70 DEG C, body
It is white emulsion form, adds 110 grams of zinc acetate（0.5 mole）, lactic acid 36g（0.4 mole）With 35 grams of trimethyl phosphate（0.25
Mole）, it is 5.5 to measure system pH, reacts 2 hours, obtains homogeneous clear liquid, be catalyst H.
The preparation of polyester
Polyester is prepared by method similarly to Example 1, catalyst is used as using catalyst H（Polyester amount based on generation）
The weight of titanium atom is 5ppm.
Test result is shown in Table 1.
【Embodiment 9】
Catalyst I preparation
Absolute ethyl alcohol 50g and tetraisopropyl titanate are added in the reactor equipped with agitator, condenser and thermometer
28.4 grams（0.1 mole）, 12.4 grams of ethylene glycol is slowly dropped into reactor（0.2 mole）, reacted 2 hours at 70 DEG C, body
It is white emulsion form, adds 128 grams of magnesium lactate（0.5 mole）, lactic acid 36g（0.4 mole）With 35 grams of triethyl phosphate（0.25
Mole）, it is 5.5 to measure system pH, reacts 2 hours, obtains homogeneous clear liquid, be catalyst I.
The preparation of polyester
Polyester is prepared by method similarly to Example 1, catalyst is used as using catalyst I（Polyester amount based on generation）
The weight of titanium atom is 5ppm.
【Embodiment 10】
Catalyst J preparation
Absolute ethyl alcohol 50g and tetraisopropyl titanate are added in the reactor equipped with agitator, condenser and thermometer
28.4 grams（0.1 mole）, 12.4 grams of ethylene glycol is slowly dropped into reactor（0.2 mole）, reacted 2 hours at 70 DEG C, body
It is white emulsion form, adds 154 grams of calcium lactate（0.5 mole）, glacial acetic acid 24g（0.4 mole）With 53.2 grams of tributyl phosphate
（0.2 mole）, it is 5.4 to measure system pH, reacts 2 hours, obtains homogeneous clear liquid, be catalyst J.
The preparation of polyester
Polyester is prepared by method similarly to Example 1, catalyst is used as using catalyst J（Polyester amount based on generation）
The weight of titanium atom is 5ppm.
【Embodiment 11】
Catalyst K preparation
Absolute ethyl alcohol 50g and tetraisopropyl titanate are added in the reactor equipped with agitator, condenser and thermometer
28.4 grams（0.1 mole）, 12.4 grams of ethylene glycol is slowly dropped into reactor（0.2 mole）, reacted 2 hours at 70 DEG C, body
It is white emulsion form, adds 154 grams of manganese acetate（0.5 mole）, glacial acetic acid 24g（0.4 mole）With trimethyl phosphate 28g（0.2
Mole）, it is 5.4 to measure system pH, reacts 2 hours, obtains homogeneous clear liquid, be catalyst K.
The preparation of polyester
Polyester is prepared by method similarly to Example 1, catalyst is used as using catalyst K（Polyester amount based on generation）
The weight of titanium atom is 5ppm.
【Embodiment 12】
Catalyst L preparation
Absolute ethyl alcohol 50g and tetraisopropyl titanate are added in the reactor equipped with agitator, condenser and thermometer
28.4 grams（0.1 mole）, 12.4 grams of ethylene glycol is slowly dropped into reactor（0.2 mole）, reacted 2 hours at 70 DEG C, body
It is white emulsion form, adds 43 grams of sodium acetate（0.5 mole）, glacial acetic acid 24g（0.4 mole）With trimethyl phosphate 28g（0.2
Mole）, it is 5.4 to measure system pH, reacts 2 hours, obtains homogeneous clear liquid, be catalyst L.
The preparation of polyester
Polyester is prepared by method similarly to Example 1, catalyst is used as using catalyst L（Polyester amount based on generation）
The weight of titanium atom is 5ppm.
【Comparative example 1】
Catalyst M preparation
Prepared according to the method disclosed in the embodiment 1 of Chinese patent application 200910171715.2.Equipped with agitator, cold
12.4 grams of ethylene glycol is added in the reactor of condenser and thermometer（0.2 mole）, the isopropyl of metatitanic acid four is slowly dropped into reactor
28.4 grams of ester（0.1 mole）, white depositions are separated out, reacts 2 hours, product is centrifuged, and use distilled water at 70 DEG C
Wash residual thing 3 times, product is dried in vacuo at 70 DEG C.Obtain white powder material.
Dried white powder material is placed in the reactor with agitator, condenser and thermometer, added
50 grams of ethylene glycol, 32 gram 25% of sodium hydrate aqueous solution（0.2 mole）, 21.4 grams of four water acetic acid magnesium（0.1 mole）, a water lemon
21 grams of lemon acid（0.1 mole）, 14 grams of trimethyl phosphate（0.1 mole）, reacted 2 hours under 150 DEG C of reaction temperatures, obtain nearly nothing
Color homogeneous liquid, is catalyst M.
The preparation of polyester
Semi-dull polyester is prepared by method similarly to Example 1, catalyst is used as using catalyst M（Based on generation
Polyester amount）The weight of titanium atom is 5ppm.
Test result is shown in Table 1.
【Comparative example 2】
Semi-dull polyester is prepared by method similarly to Example 1, catalyst is used as using antimony glycol（Based on generation
The amount of polyester, the weight of antimony atoms is 250ppm）.
Test result is shown in Table 1.
Table 1
【Embodiment 13~24】
Catalyst stability is tested
Catalyst A~L in above-described embodiment is respectively taken into 50g, loaded in transparent sealing vial, in insolation under sunburst
One week.
Semi-dull polyester is prepared by method similarly to Example 1, using the above-mentioned catalyst after being exposed to the sun as catalyst
（Polyester amount based on generation, the former weight of titanium is 5ppm, and the weight of antimony atoms is 250ppm）.
Test result is shown in Table 2.
【Comparative example 3~4】
Catalyst stability is tested
Catalyst in above-mentioned comparative example 1, comparative example 2 is respectively taken into 50g, loaded in transparent sealing vial, in sunburst
Lower insolation one week.
Semi-dull polyester is prepared by method similarly to Example 1, using the above-mentioned catalyst after being exposed to the sun as catalyst
（Polyester amount based on generation, the former weight of titanium is 5ppm, and the weight of antimony atoms is 250ppm）.
Test result is shown in Table 2.
Table 2
As the above results we it can be found that the semi-dull polyester property indices prepared by catalyst of the present invention are all bright
The aobvious semi-dull polyester being better than in comparative example prepared by catalyst, therefore catalyst preparation semi-dull polyester of the present invention has uniqueness
Superiority.
Claims (10)
1. a kind of titanium series polyester catalyst, the reaction product of 0.5~10 hour is reacted at 0~200 DEG C by following raw material
Obtain：
(A) there is the titanium compound of below general formula
Ti(OR)4
R is the alkyl selected from 1~10 carbon atom；
(B) it is selected from the dihydric alcohol with 2~10 carbon atoms；
(C) a kind of metal salt compound in IA, IIA, VII B, II B in the periodic table of elements；
(D) selected from least one of organic acid aliphatic organic acid；
(E) selected from least one of phosphorus compound phosphate compound；
Wherein, the mol ratio of dihydric alcohol (B) and titanium compound (A) is 1~20: 1；Metal salt compound (C) and titanium compound (A)
Mol ratio be 0.1~20: 1；The mol ratio of aliphatic organic acid (D) and titanium compound (A) is 0.1~20: 1；Phosphation
The mol ratio of compound (E) and titanium compound (A) is 0.1~10: 1；The pH value of reaction system is controlled 4.5~6.5.
2. titanium series polyester catalyst according to claim 1, it is characterised in that titanium compound (A) be selected from tetramethoxy titanate ester,
At least one of tetraethyl titanate, metatitanic acid orthocarbonate, tetraisopropyl titanate or butyl titanate.
3. titanium series polyester catalyst according to claim 1, it is characterised in that dihydric alcohol (B) is selected from ethylene glycol, 1,2- third
At least one of glycol, 1,4- butanediols or 1,6-HD.
4. titanium series polyester catalyst according to claim 1, it is characterised in that metal salt compound (C) be selected from lithium, sodium,
One kind in zinc, manganese, magnesium, the salt of calcium.
5. titanium series polyester catalyst according to claim 1, it is characterised in that aliphatic organic acid (D) be selected from citric acid,
At least one of glacial acetic acid, tartaric acid, oxalic acid or lactic acid.
6. titanium series polyester catalyst according to claim 1, it is characterised in that phosphate compound (E) is selected from tripotassium phosphate
At least one of ester, triethyl phosphate, tricresyl phosphate propyl ester, tricresyl phosphate isopropyl ester, tributyl phosphate or triphenyl phosphate.
7. titanium series polyester catalyst according to claim 1, it is characterised in that dihydric alcohol (B) rubs with titanium compound (A's)
You are than being 1~4: 1；The mol ratio of metal salt compound (C) and titanium compound (A) is 1~10: 1；Aliphatic organic acid (D) with
The mol ratio of titanium compound (A) is 1~10: 1；The mol ratio of phosphate compound (E) and titanium compound (A) is 5~10: 1.
8. titanium series polyester catalyst according to claim 1, it is characterised in that raw material also includes (F) and is selected from 2
The mol ratio of the monohydric alcohol of~10 carbon atoms, monohydric alcohol (F) and titanium compound (A) is 1~20: 1.
9. titanium series polyester catalyst according to claim 8, it is characterised in that monohydric alcohol (F) rubs with titanium compound (A's)
You are than being 1~10: 1.
10. a kind of method for producing semi-dull polyester, using dicarboxylic acids and dihydric alcohol as raw material, in the titanium described in claim 1
It it is 230~280 DEG C in reaction temperature in the presence of series polyester catalyst, reaction pressure is progress under conditions of normal pressure~0.5MPa
Esterification, obtains esterification products, is then 250~320 DEG C in reaction temperature, reaction pressure is the vacuum bar less than 150Pa
Progress polycondensation reaction obtains addition titanium dioxide in polyester product, course of reaction and is used as delustering agent under part.
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| CN105218798A (en) * | 2014-07-03 | 2016-01-06 | 中国石油化工股份有限公司 | The preparation method of half delustring Poly(Trimethylene Terephthalate) |
| CN109208098B (en) * | 2017-07-06 | 2021-09-10 | 中国石化仪征化纤有限责任公司 | Fluorescent whitening agent, master batch and preparation method of titanium series whitening polyester staple fiber |
| CN109232865B (en) * | 2018-08-08 | 2020-12-15 | 济南朝晖科技有限公司 | Titanium-containing composition and preparation method and application thereof |
| CN108976403B (en) * | 2018-08-08 | 2021-01-12 | 济南朝晖科技有限公司 | Process for producing polyester |
| CN110117356A (en) * | 2019-05-21 | 2019-08-13 | 中国石油化工股份有限公司 | A kind of preparation method and application of carboxy lower composition containing weight polyester and composition solution |
| CN114479038A (en) * | 2020-10-23 | 2022-05-13 | 中国石油化工股份有限公司 | Titanium catalyst and preparation method and application thereof |
| CN114790282B (en) * | 2021-12-30 | 2023-03-21 | 康辉新材料科技有限公司 | Preparation method and application of nano-microparticle in-situ polymerization catalyst |
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| CN102219894A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for producing semi-dulling titanium series polyester |
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| CN1644601A (en) * | 2004-12-29 | 2005-07-27 | 中国石化集团天津石油化工公司 | Preparation of liquid titanium polyester polycondensation catalyst |
| CN102219894A (en) * | 2010-04-15 | 2011-10-19 | 中国石油化工股份有限公司 | Method for producing semi-dulling titanium series polyester |
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